JPS627040A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To enhance the sensitivity of a photographic emulsion by incorporating in the photographic emulsion, grains obtained by jointing silver halide crystals high in the content of silver bromide with host crystals in a protruding state, and a substance having adsorptivity to silver halide. CONSTITUTION:Face-centerd cubic crystals consisting of silver chlorobromide, iodochloride, iodochlorobromide, or the like containing silver chloride or this silver chloride as a solid solution are used as the host crystals. The face- centered cubic crystals of silver halide grains higher inn the content of silver bromide than the average of the total silver halide grains are jointed in protruding forms as guest crystals with the corner or edge of each of the host crystals. The emulsion of the titled contains the silver halide grains of said structure and the substance having adsorptivity to silver halide, such as a spectral sensitizing dye of a cyanine dye, thus permitting the obtained photographic emulsion to be made higher in sensitivity than the host grains.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic emulsion and its manufacturing method, and includes silver halide grains containing silver chloride or silver chloride as a solid solution, such as silver halide grains containing silver chloride as a solid solution. silver oxide, silver iodochloride,
The guest crystals, which have a higher silver bromide content than the host crystals, are bonded to the corner portions and/or edges of the host crystals in a protruding manner to the host grains, such as silver iodochlorobromide. Our goal is to provide high quality photographic emulsions.

(Prior art) Silver halide crystal grains are exposed to visible light and ultraviolet light or
It is well known in the field of photography that radiation such as radiation, neutron beams, gamma rays, etc., is useful for forming latent images and developing them to form visible images. Examples of such silver halide include silver iodide, silver bromide, silver chloride, silver iodobromide, silver iodochloride, silver chlorobromide, and various silver halide crystal grains mainly composed of silver iodochlorobromide. It is used. In addition, the shapes of these silver halide crystal grains range from regular crystal grains such as cubes, octahedrons, tetradecahedrons, and dodecahedrons to irregular crystal grains such as spherical, tabular, and irregular shapes. Crystal grains with a multiphase structure having a layered structure or a bonded structure are even known. The fact that the halogen composition, shape, and structure of the grains are greatly involved in the properties of the silver halide grains is due to T, H,
"The Theory of..." by James
The Photographic Process J
ry of the photography
process) Mμ version Macmillan Co, Ltd, New York
This is not only clear from the descriptions and descriptions of the properties of silver halide in Chapter 7 and Chapter 3 of Chapter 3, and the description of the formation of silver halide in Chapter 3, but also well known to those skilled in the art. be.

The halogen composition, grain shape, grain size, and grain size distribution of the silver halide emulsion are selected and adjusted appropriately depending on the purpose of use and the performance to be imparted to the photographic light-sensitive material using the emulsion. However, it is not always possible to obtain silver halide grains that fully satisfy the required performance, and it is a matter of concern to those skilled in the art as to how to obtain an emulsion that fully satisfies the desired performance. be.

For example, in terms of photographic performance, high sensitivity, low fog, excellent graininess, and rich gradation are expected, and in terms of processing performance, speed and stability are expected, as well as excellent stability over time and pressure resistance. It is expected that there will be.

Many techniques are known that utilize the characteristics of these various silver halides. There are many descriptions regarding the core-shell layered structure of silver halide grains in various literatures. Typically, the core is coated over its entire surface with one or more shells of different silver halides.

Special public Akira! 6.7g No. 3 has an emulsion containing silver bromide in the core and silver chloride in the shell, which has both the high photosensitivity of silver bromide and the rapid developability of silver chloride, but mixed crystal silver chlorobromide It is stated that the advantageous effects of both are suppressed in emulsions. In addition, according to West German Patent Application Publication (OLS) 3°2.2, the Tatata has at least a silver halide layer having a silver chloride content of 2 g molti adjacent to a silver halide layer having a lower silver chloride content. It is disclosed that the core-shell silver halide grains produced by this method are characterized by low fog and good pressure resistance.

On the other hand, several techniques are known regarding silver halide crystal grains having a structure different from the core-shell structure. Namely, U.S. Pat.

No. 6tμ discloses an emulsion containing silver halide grains obtained by bitaxially growing silver chloride on polyhedral silver iodide. Furthermore, US Patent μ/<4λ OO discloses silver halide grains in which silver chlorobromide is bonded to polyhedral silver iodide. Also, aspect ratio r:
A photographic emulsion in which silver chloride is epitaxially grown on tabular silver iodide host grains larger than l, and a photographic element using the emulsion are disclosed in JP-A-Sho! Tarl/ri 3μ≠ issue and Tokukaisho! It is disclosed in Tarl/Re 3JrO.

Furthermore, grains in which silver bromide or silver iodobromide are epitaxially bonded to silver iodide polyhedral crystals are disclosed in JP-A-3J-/ls3!
No. 32, and grains in which silver chloroiodobromide was epitaxially bonded to silver iodide polyhedral crystals were published in JP-A-63-/μ Tata 34c.
In JP-A No. 11, 1987, grains in which silver bromide or silver iodobromide consisting of silver iodide polyhedral crystal K(111) planes were epitaxially bonded were published. -2773μ.

JP-A No. 33-6/22, silver iodide content 13~
This publication discloses grains in which silver halide having a silver iodide content of less than 1O Morch is epitaxially bonded to silver iodobromide of Hiro O Morch.

Japanese Patent Application Laid-Open No. 31-10IJ' discloses grains characterized in that silver salts are arranged on selected surface regions of tabular halogenated grains whose host grains have an aspect ratio greater than r:/.
It is disclosed in No. 24.

In addition, K, a halogen in which a guest crystal containing less iodide than the host grain is epitaxially grown on a silver halide grain containing iodide with an aspect ratio of less than 227 and the host grain contains (111) rIrJ by limiting the site of the host grain. Silveride photographic emulsions are disclosed in US Pat.

US Pat. No. 710!0 discloses an emulsion consisting of a silver halide host grain having a face-centered cubic crystal structure and a non-isomorphic silver salt grown only at the edges and corners of the host grain.

Furthermore, in Japanese Patent Publication No. 2 μ772, silver chloride or chlorobromide was bonded to the surface of the (III) face of silver iodobromide tetradecahedral grains with a silver iodide content of 20 molt or less, although the bonding was not in the form of protrusions. Cubic particles grown with silver are disclosed.

As these examples show, conventional EvitaCal emulsions have the same face-centered cubic crystal structure as the host and guest crystals, and are characterized by the host grains being relatively less soluble than the guest crystals. . If, on the contrary, we can obtain bonded grains in which the guest crystals of silver halide are less soluble than the silver halide in the host crystals, in addition to the fast deterioration properties inherent in the host grains, in addition to the properties of silver halide,
Since the absorption long wavelength edge of more poorly soluble salts is longer,
Since the light absorption region is expanded, more photons are absorbed by the guest crystal, and photoelectrons flow into the host crystal, which is expected to concentrate the latent image and increase sensitivity.

By the way, Klein et al.
denz) 102! At the (i966) I/C,
Report the shape and photographic properties of silver bromide emulsion coatings immersed in potassium iodide aqueous solution for halogen substitution, and silver chloride emulsion coatings immersed in potassium bromide solution for halogen substitution. There is. They found that when an octahedral silver bromide coating was immersed in a potassium iodide solution, silver iodide bonded to the corners and edges in protrusions, but cubic silver bromide and chloride In the case of silver, it was a random substitution with no particular site selectivity. Furthermore, Shiozawa said,
Bulletin of Research, Photographic Science and Technology of Japan (Bulletin of 5ociet)
yof photography 5science
andTechnology of Japan
n) 22/Hiro (/ri72), a coating film of a cubic silver chloride emulsion was coated with a potassium bromide solution saturated with silver bromide.
It has been reported that silver bromide is bonded to the corner and edge portions of cubic silver chloride by halogen conversion by immersion in IN for 64 A minutes. However, it is impossible to produce photographic light-sensitive materials in large quantities by such a method, and since the system is inherently unstable, these materials are not suitable as practical light-sensitive materials. On the other hand, even if an attempt is made to produce stable grains in which silver halide guest crystals, which are less soluble than host grains, are bonded to specific parts, by a known emulsion manufacturing method, halogen substitution method in a liquid emulsion system, the method described by Zuckerman K. Journal of Photographic Science)
al of photography 5ci
ence)21A/≠2 (/76), it is extremely unstable, and it is usually not possible to selectively and stably bond silver halide, which is less soluble than the host grain, to a specific site. This means that although there have been many reports on emulsion manufacturing methods using halogen substitution for a long time, emulsion grains with poorly soluble silver halide selectively bonded to corners and edges are easily understood.

One reason for this is that, in general, such bonded grains are extremely thermodynamically unstable, so conventionally known epitaxial growth techniques and halogen substitution methods cannot produce emulsions that can be stably used as practical photographic emulsions. This seems to be due to this.

(Objective of the Invention) The object of the present invention is to bond a silver halide crystal with a higher silver bromide content to a specific part of silver chloride and/or a silver halide mixed crystal containing silver chloride as a solid solution, thereby stabilizing the shape. Another object of the present invention is to provide a photographic emulsion containing silver halide grains that achieves high sensitivity.

(Means for Solving the Problems) As a result of intensive research, the present inventors have found that the object of the present invention is to provide silver chloride and/or face-centered cubic silver halide mixed crystal host emulsion grains containing silver chloride as a solid solution. For silver halide grains and grains in which face-centered cubic silver halide crystals with a silver bromide content higher than the average of all silver halide grains are joined to the corner portions and/or edge portions of the host crystal in a protruding manner, It has been found that this can be achieved by using a silver halide photographic emulsion containing a substance that has adsorption properties.

First, the present inventors introduced bromine ions into a liquid emulsion of silver chloride or silver halide mixed crystal grains containing silver chloride, and added an adsorbent midway through the process to freeze the grain shape while tracking the halogen conversion process. I tried to do that. In other words, when an aqueous potassium bromide solution is added to the host emulsion, guest crystals containing a high concentration of silver bromide begin to grow at the corners or edges of the host grains, thereby replenishing the consumed silver ions in the solution. Therefore, other parts of the host particles are dissolved, and the eluted ions immediately react with bromine ions to continue the growth of the guest crystal.

By repeating this process, guest crystals continue to grow until most of the bromide ions in the solution are consumed.

Subsequently or simultaneously by recrystallization.

We discovered that once the bonded particles are formed, they quickly deform and become the well-known amorphous halogen-substituted particles. The reason why such a halogen conversion process has not been observed so far is probably because the halogen conversion process itself occurs relatively quickly and no attempt has been made to stop recrystallization. .

The present inventors have discovered that by using an adsorbent substance on the bonded particles once generated through halogen conversion, the dissolution of the particles is stopped and unstable bonded particles are deformed by recrystallization. We succeeded in stably obtaining .

The bonded halogenated aluminum particles of the present invention will be explained in detail below.

The halogen composition of the host crystal is silver chloride or silver chlorobromide containing silver chloride as a solid solution, silver iodochloride, silver iodochlorobromide, or the like. In the case of silver chlorobromide/silver iodochloride and silver iodochlorobromide, the content of silver chloride is preferably 20 molti or more. In the case of silver iodochloride or silver iodochlorobromide, the content of silver iodide is desirably less than io mole.

The halogen composition of the guest crystal can be silver bromide, silver chlorobromide, silver iodobromide, and silver iodochlorobromide, as long as the silver bromide content is higher than the average of all silver halide grains. The silver iodide content of silver iodobromide and silver iodochlorobromide is preferably 10 molti or less.

The most typical forms of host crystals used in the present invention are cubic dodecahedron (consisting of (100) and (111) planes) and octahedral dodecahedron (consisting of (110) planes). ), - It is desirable that corners and edges clearly appear in polyhedra surrounded by clear planes such as heavy twins and double twins. More preferably, the particles are regular particles such as cubes, tetradecahedrons, octahedrons, and dodecahedrons with good monodispersity, in which the ratio of the standard deviation of the particle size distribution to the average diameter is within 0.3. . In addition, the average size of the host particles is O,OSμ in terms of spherical particles having the same volume.
m or more and 3 μm or less, preferably 0. % is preferably in the range of /μm or more and λμm or less.

The guest crystals joined to the corner portions and/or edges in a protruding manner may be regular shapes such as cubes, tetradecahedrons, octahedrons, and dodecahedrons, or irregular shapes such as spherical or irregular shapes. , regardless of the shape.

The bonded guest crystals are bonded to the corner and/or edge portions of the host crystal in a protruding manner, and the silver bromide content of the guest crystals is higher than the average silver bromide content of the entire bonded grains produced. is a feature.

The average size of the produced bonded particles is preferably 0.1 μm or more and 0.2 μm or less, especially 0.2 μm or less, based on the diameter of a sphere with the same volume.
More preferably, the thickness is not less than μm and not more than 25.3 μm.

The molar ratio between the silver halide in the guest crystal bonded to the host crystal and the silver halide in the remaining host crystal can be set arbitrarily, but if this ratio is too large, the guest crystal will not be able to fully bond and will split into separate In some cases, particles are formed, or particles with a double structure in which the bonding structure is hidden by completely covering the entire surface of the host crystal may be formed. Therefore, this ratio is preferably 3 or less, particularly preferably less than 7, in terms of silver molar ratio.

Next, a method for preparing the bonded emulsion grains of the present invention will be described.

Formation of bonded particles begins with the preparation of host crystals. Cubic grains, tetradecahedral grains, octahedral grains, or twin grains can be prepared by adding a soluble silver salt aqueous solution and a soluble halogen salt aqueous solution under conditions where the silver ion concentration is constant. When the silver chloride content is high, it can be formed without keeping the silver ion concentration constant. Also"
Physical Chemistry Bunsen Society Report” Volume 67 (/ri1?) KE
.

Moisar and Klein, E.
) may also be formed by a method such as that described by. Alternatively, a one-sided mixing method, a combination of a simultaneous mixing method and a one-sided mixing method may be used. If the host particle has the above-mentioned halogen composition on the particle surface or shell portion, the particle interior or core portion may have a different halogen composition, even if it has a so-called double structure type or other structure. I can't help it.

Further, a mixed emulsion of two or more types of monodispersed grains having different average sizes, halogen compositions, crystal phases, etc. may be used.

The introduction of guest crystals can be achieved by adding soluble bromide to a tank containing host crystals to cause halogen conversion, and at that stage, suppressing the deformation of the bonded emulsion grains due to recrystallization once formed using an adsorbent substance. . At that time, other soluble halides and/or soluble silver salts may be added along with the addition of soluble bromide.

When no soluble silver salt is added, the amount of soluble bromide added is 7! It is preferably less than 100 ml. This is because when soluble silver salt is not added, silver ions are supplied from the host crystal for guest crystal formation, but if soluble bromide is added in excess of the above amount, the host crystal becomes thin due to dissolution etching, etc., and guest crystals no longer exist. This is because it may become impossible to bond and hold the crystal to the host crystal. Further, at this time, other water-soluble halides may be added. Particularly in the case of soluble iodides, it is desirable that the amount of silver in the host grains be 10 moles or less. When adding a soluble silver salt aqueous solution together with a solution containing soluble bromide, it is preferable that the soluble silver salt is less than 5"O mol of the silver content of the host crystal. This is because adding more than the above amount will damage the surface of the host crystal. This is because particles tend to be covered and have a double structure.Furthermore, in this case, the amount of soluble silver salt must not exceed the equivalent amount of soluble bromide to be added. When adding soluble bromide, the excess amount is desirably less than !θ morti of the silver chloride content of the host crystal.

Incidentally, in this halogen conversion operation, the rate of addition of soluble bromide and the timing of addition of the adsorptive substance after addition are particularly important factors in preparing this type of conjugated particles. This is because recrystallization generally progresses simultaneously with the growth of guest crystals, and only when the growth rate of guest crystals is sufficiently large compared to the dissolution rate of guest crystals during recrystallization, the bonded emulsion This is because particles are formed. This recrystallization continues during and after the addition of soluble bromide, and the rate of deformation caused by this is influenced by the solubility of the guest crystal, the particle size, the halogen composition of the host crystal, the temperature of the system, etc.

Therefore, depending on the system conditions, the adsorbent is added at an appropriate time before recrystallization progresses excessively and the particles turn into amorphous particles. Usually added after the addition of soluble bromide, the purpose of this adsorbent substance is to suppress the grain deformation caused by recrystallization of the bonded emulsion grains once formed, so the growth of guest crystals is significantly suppressed. If not, it may be added before the addition of the soluble bromide, or it may be added in several portions or continuously from before to after the addition of the soluble bromide.

In the present invention, the term "substance adsorbent to silver halide" refers to a substance other than gelatin which is adsorbent to silver halide crystals.

As such adsorbent substances, the spectral sensitizing dyes shown below are effective.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a corchioxazolidine-2,
4cm dione nucleus, thiazolidine-2,IA-dione nucleus,
A J-6 membered heterosegmental ring nucleus such as a rhodanine nucleus or a titanium barbile nucleus can be applied.

Useful sensitizing dyes include, for example, German patents λ and o.
tro, U.S. Pat. No. 2,23/, 1SJR, U.S. Pat. μ
J, No. 744g, No. 2.303.77A, No. 2. j
/ri, 00/issue, same 2. ri/2,3λri number, 3,13
6. Rijri No. 3,672゜tri No. 7, No. 3,6riμ
, No. 217, μ, 02j, No. 3'A, No. 4c, 01
A6.172, British Patent/, 21A2.311,
Special public Sho 4c44-/1AO30, same J:2-21A
Various dyes described in IIA≠ can be mentioned.

These dyes may be used alone or in combination with the above. Further, it may be a dye that itself does not have a spectral sensitizing effect, a substance that does not substantially absorb visible light, or a substance that exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (eg, US Patent λ).

ri 33, 3 ri 0, ri 3, 63! , No. 7.2/), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,7143,610), and the like.

In addition, the adsorbent substances include the following compounds used in the art as antifoggants or stabilizers, such as azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzo-IJ azoles, etc. , benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-monomercapto); tetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (particularly hydroxy-substituted (i
e 3+3a, 7) tetraazaindene); benzenethiosulfonic acids; and further, nucleic acid decomposition products such as adenine and guanine are also effective.

Polymers containing repeating units alone or in combination, such as polyvinyl alcohol and polyvinylpyrrolidone, are also effective as adsorbent substances. Or tetrazole! −
Thiol derivative, /, 2. ≠-triazolo (/, j-a
) Polymers containing repeating units containing pyrimidine residues, benzotriazole residues, etc. are also effective. Examples of these are U.S. No. 3236qoi, JP-A-37-2/l/
μλ, as disclosed in Japanese Patent Application Laid-Open No. 2003-100000g4cμ.

Furthermore, heavy metal ions such as cadmium ions, zinc ions, thallium ions, iridium ions, lead ions, and iron ions are effective as adsorbent substances. These adsorbent substances may be used not only alone but also in combination.

As adsorbent substances, we found inter alia merocyanine for sensitizing dyes, l-phenyl-y-mercaptotetrazole, μm hydroxy-6-methyl-(l) for antifoggants and stabilizers.

It has been found that lead ions are effective in suppressing recrystallization of j, Ja, 7)-tetraazaindene, nucleic acid decomposition products, and heavy metals. In particular, spectral sensitizing dyes are preferably used in the sense that they can prevent recrystallization and at the same time increase photographic sensitivity.

Such adsorbed substances generally have side effects such as inherent desensitization and development inhibition, and therefore, the amount added is preferably around the minimum amount that can substantially suppress recrystallization of the guest crystals.

For example, for a spectral sensitizing dye, 1oo of saturated coverage
If it is added to the vicinity of s, it often causes inherent desensitization and adversely affects photographic properties, as described in [The Theory of the Photographic Process J] by T. H. James. (The Th
theory of thephotographic
process) 1st edition Macmillan @2, :L-”
! -ri (Macmilfan Co.

Ltd, New York) (7) Chapter 10 has been described, and in the present invention, the saturation coverage is 50 to 73.
% is most preferably used.

In this way, it is possible to use adsorbent substances without deteriorating the photographic properties. Therefore, it is possible to use adsorbent substances without deteriorating the photographic properties. Stable bonding of silver bromide, silver chlorobromide, silver iodobromide S, and silver iodochlorobromide guest crystals with a higher silver bromide content than average to the corner and/or edge portions of the host crystal in the form of a protrusion. The expected increase in sensitivity was achieved by obtaining emulsion grains with a high sensitivity.

Although there is no particular restriction on the proportion of particles joined in the form of protrusions in the present invention, it is preferably at least SO% of the total number of particles. More preferably, the roe is 4 or more.

For this reason, it is desirable that the host crystals have good monodispersity in size, and the higher the stirring efficiency during addition of soluble bromide, the easier it is to obtain bonded particles with a small interparticle distribution and excellent photographic properties.

The silver halide emulsions of the present invention are usually chemically sensitized.

In other words, sulfur sensitization using sulfur-containing compounds (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin and silver, reducing substances (
For example, reduction sensitization using stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (for example, gold compounds, as well as metals from group Ⅰ of the periodic table such as platinum, iridium, and noradium). A noble metal sensitization method using complex salts of 1 to 4 can be carried out alone or in combination.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Various compounds can be contained for the purpose of preventing fog during storage or photographic processing, or for stabilizing photographic performance. Namely, azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promohenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g., mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (in %/-phenyl-j-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.); e.g. Thioketo compounds; azaindenes (e.g. triazaindenes, tetraazaindenes (specially KIA-hydroxy substituted
/, 3.3a, 7') tetraazaindenes), pentaazaindenes, etc. 1; Known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds can be added.

For more detailed examples of these and how to use them, see, for example, US Patent No. 3. the law of nature! Hiroshi, ≠ 7th issue, same 3. Riza! , Rihiro No. 7, Tokko Sho J2-2G, No. 660 can be used.

The photographic light-sensitive material using the emulsion of the present invention is a color image-forming coupler, that is, a color is developed by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) during color development processing. It may contain a compound that absorbs water. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a pallast group in its molecule, or a polymerized coupler. The coupler may be either da-equivalent or λ-equivalent to silver ions. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The product of the coupling reaction may also be colorless and include a colorless DIR coupling compound that releases a development inhibitor.

For example, magenta couplers include j-virazolone couplers, pyrazolopenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides,
Examples of cyan couplers include naphthol couplers and phenol couplers.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (
(e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauryl ester), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. trimesine), or organic solvents having a boiling point of about 300C to 1JO0C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-22-hand xyethyl acetate, methyl cellosolve, etc. After dissolving in acetate etc., it is dispersed in hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

For photographic processing of light-sensitive materials using the emulsion of the present invention, any known method can be used, and known processing solutions can be used. In addition, the processing temperature is usually /
The temperature is selected between f'c and 5o0c, but the temperature may be lower than /♂00 or higher than 5o0c. Depending on the purpose, development processing to form a silver image (black and white photographic processing),
Alternatively, any color photographic process consisting of a development process to form a dye image can be applied.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, ≠-
Amino-N, N-diethylaniline, 3-methyl-μm
Amino-N, N-diethylaniline, μm amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-ami/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-N
-β-methanesulfamide ethylaniline.

μm amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press, C/
91,1. p. 226-2, US Pat. ois issue, same co, 392, 36≠ issue, JP-A-4
Those described in Lzaichi No. 614Y33 may also be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. Depending on the requirements, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, and quaternary ammonium j3 [%
Development accelerators such as 7mi7[1, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifying agents, U.S. Patent IA, 013° Polycarboxylic acid chelating agent described in No. 723, OLS
, 2, 6.2j, RI No. 10, etc. may also be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (1), cobalt (1), chromium (V
1), compounds of polyvalent metals such as copper (If), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron (1) or cobalt (1), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /, 3-diamino-2-propatoltetraacetic acid, etc. Alternatively, complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfates, permanganates, nitrosophenols, etc. can be used. Among these, potassium ferricyanide, sodium ferric(1) ethylenediaminetetraacetate, and ammonium iron(1) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron(1) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Bleach or bleach-fix solutions are described in U.S. Patent 3. OIAλ, 6
No. 20, copper 3,2≠l, No. 766, special public show ttr-rs
In addition to the bleaching accelerators described in Japanese Patent Publication No. 4Ls-1136 and the like, and the thiol compounds described in Japanese Patent Application Laid-Open No. 63-1SJ7.32, various additives can also be added.

There are no particular restrictions on other constituent elements of the photographic light-sensitive material using the silver halide emulsion of the present invention.
clusure) / Volume 76RD-/761A3C/
971/72) and same/r7 volume RD-/17/A(/
(January 2010) can be referred to.

The locations where various additives are described in the above research disclosure are shown below.

Additive type RD17643 RD18716
1 Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer Pages 23-24 Page 648 right column - Super sensitizer Page 649 right column 4 Anti-fogging agent Page 24-25 Page 649 right column and stabilizer 5 Light absorber, film 25- Page 26 649 Right column ~
Ilter dye 650 left column UV absorber 6 Stain prevention page 25 right column 650 left to right column 7 Hardener page 26 651 page left column 8 Binder page 26 Same as above 9 Plasticizer, lubricant page 27 650 right column 10 Coating auxiliary agent,
Table: Pages 26-27 Same as above Surface active agent 11 Static prevention Page 27 Same as above The present invention will be further explained with reference to the following examples.

Example/ Host emulsion A was prepared according to the following procedure.

Sodium chloride O to 100ml of inert gelatin 3T aqueous solution
, OtAmol was added and pHj was adjusted by 1 m,
While maintaining the preparation temperature at 70oC, silver nitrate/mol/ml solution Roog and aqueous solution Roo111 containing 0 μmol of potassium bromide and 1≠fmol of sodium chloride were simultaneously added to a well-stirred tank at a uniform rate over 10 minutes.

This emulsion is AgBro, 5c, with an average equivalent sphere diameter of O0jμm.
to 15 cubic particles. pα/, 26. However, the equivalent sphere diameter means the diameter of a sphere with the same volume.

j00cI/C maintained host emulsion A ((a) in Figure 1)
) to sublimated potassium O0♂! Mol/n solution! Nod (equivalent to 10 mol. In addition, redispersion was performed at 4to0c to reduce the silver halide concentration to O0.
≠lAmol/emulsion gelatin f”/concentrate 10.211
/Tb pHl, 20. pC12VC was adjusted. This is the comparative emulsion EM-/. When observed with an electron microscope, irregularly shaped particles were found. (Figure 1(b))'
! In addition, the X-ray diffraction profile of the C220) plane of silver halide in face-centered cubic grains measured by CuK1 ray shows that the silver bromide content is 3.
There is a peak at 0 mol% and a second peak at 70 mol%. However, the silver bromide content shown here is T and H.

The Theory of the Photographic Process by James
theory of the photography
icprocess) 1st edition Macmillan Co, New York (Macmillan Co, I, tdJJew Y
This corresponds to the change in the lattice constant as a function of the silver bromide content of the silver chlorobromide mixed crystal shown in Chapter 1, Section 1 of the Ork).

In the same manner, after adding the potassium bromide solution, a 30 mm methanol solution of dyestuff was added to a sand diameter of 30 mm, allowed to stand for 1 minute, and then washed with desalted water and redispersed. This is BM-2 of the present invention. It can be seen from the electron micrograph and X-ray diffraction profile that the silver chlorobromide of silver bromide was bonded to the corners of the host cubic grains in a protruding manner. (Figure 7(d)
, 2) The reason why the halogen composition of the guest grains is not pure silver bromide is considered to be that some recrystallization occurs even during the formation of bonded guest grains.

The X-ray diffraction profiles of dye host emulsions A, EM-/and EM-2 are shown in FIG.

Under the same preparation conditions as Example λ EM-, 2, the potassium bromide aqueous solution was added over a period of 7 minutes, and at the same time as the addition of potassium bromide was completed, a 34 cOd/mM methanol solution of dye A was added.
1 was added, and after 7 minutes, demineralization, washing with water, and redispersion were performed. This emulsion is designated as EM-j.

It was confirmed from electron micrographs and X-ray diffraction profiles that EM-j is a particle in which silver bromide containing some silver chloride is bonded to the corner of the host particle in a protruding manner, similar to EM-1.

Example 3 O, rμm o 1 / j under the same preparation conditions as EM-2
! Potassium bromide aqueous solution ≠7.3″d, /Od, 23
7.6yd, λIjd, JIOd, ≠7jd. The ratio of bromide ion to the chlorine content of the host emulsion grains is 1Omolti, μOmolti, 10molti, and 60molti, respectively, and the emulsions EM-μ, EM-j, and
EM-4 and EM-7. In addition, this ratio of EM-j is λO morti.

Electron micrographs of these emulsions show that when this ratio exceeds jOmolti, the host grains are severely etched when bonded grains are formed by halogen conversion, resulting in grains that are no longer able to hold the grown guest grains. It was observed that the difference between particles in the morphology of bonded particles began to appear and became larger.

The temperature was ≠0°C15o under the same preparation conditions as Example Emulsion EM-2.
After adding potassium bromide aqueous solution at each temperature, at ≠ o 'C, 30 seconds later, 7 minutes and 30 seconds later, 3
Minutes later, 4 tocr of the emulsion was sampled and /-phenyl-! -Mercaptotetrazole C (hereinafter abbreviated as PMT) 0. /mM methanol solution aoct:.

was added to stop recrystallization associated with halogen conversion.

Regarding zooc, the IcPMT methanol solution sampled after 30 seconds and 1 minute and 30 seconds was added.

From the electron micrograph of the emulsion thus obtained, it was observed that as the temperature decreases, the growth rate of AgBr guest grains due to halogen conversion slows down, and that even if the timing of PMT addition is delayed, bonded grains are formed without deformation. It was done.

Furthermore, in 1Ao0c and j-0'CK, PMT was found to have stable conjugated particles as well, similar to dye (3).

Example! The dependence of the silver chloride content of host grains is shown. A method for preparing the host emulsion grains of emulsions B, C, and D, which are pure silver chloride cubic grains and silver chlorobromide grains with a silver chloride content of to molti and 2j molti, respectively, will be described. The average equivalent sphere diameter of each emulsion was O.S .mu.m.

Emulsion B: Add 100 dl of inert gelatin aqueous solution and 0.0/l Amol of IC sodium chloride, adjust the pH to 3 and 6, and add silver nitrate/mol while maintaining the preparation temperature at 70' CIC.
/JL solution 100d and sodium chloride 0°127mol
A solution containing ♂00- and ♂00- were simultaneously added at a constant speed over j0 minutes to a tank that was being well stirred at 700 rpm. Thereafter, the same pα/ and 2AKNaα as in emulsion A were added for adjustment. Emulsion B thus obtained is a pure silver chloride cubic grain emulsion.

Emulsion C 3% aqueous solution of inert gelatin ♂00d with 0 sodium chloride
．． After adding 027 mol and adjusting the pH to A, silver nitrate/mol/J2 solution room, potassium bromide O1/Amol and sodium chloride 0.6? A solution 1f00rd containing jmO1,
The SO was simultaneously added at a uniform rate over the course of the batch into a well-stirred tank.

Thereafter, Naα was added to the same pα/2 as in Emulsion A for adjustment. Emulsion C thus obtained is a silver chlorobromide cubic grain emulsion with a silver chloride content of 0 mol.

Emulsion: 100 d of inert gelatin 3% aqueous solution with 0 sodium chloride
．． After adding 0/1 Amol and adjusting the pH to 3, A,
Silver nitrate/m O1/ while keeping the preparation temperature zo0c
It solution room and solution ♂00d containing 0.60 ml of potassium bromide and 0.223 mol of sodium chloride were simultaneously added to a well-stirred tank at a uniform rate over 30 minutes, washed with desalinated water, and then added with inert gelatin.・Add phenol and water and redisperse until the silver halide concentration is 0.
．． 67mol/Kp, gelatin concentration 7/, ly/
Adjusted to Kp. 1 zoy of this emulsion was weighed, 0.002 mol of sodium chloride, inert gelatin and water were added and dissolved in VC to give a gelatin concentration of 3ts and a pH of #%100xtK. Thereafter, while maintaining the temperature at 7j'C, an aqueous solution ♂00d containing 0.7mol of silver nitrate, 0.62jmol of potassium bromide, and 0.0d of sodium chloride were added. /ri2mo
100 d of an aqueous solution containing 1 was simultaneously added at a constant speed over 30 minutes while stirring well in a tank. Thereafter, the same pC1/26KNaα as in emulsion A was added for adjustment.

The emulsion thus obtained is a silver chlorobromide cubic grain emulsion with a silver chloride content of λj.

Under the same preparation conditions as EM-2, a solution of 6 μmol/g of potassium bromide O was added to emulsions B, C, and D, and recrystallization was stopped using dye A. ,i
o. The result of the electron micrograph X-ray diffraction profile shows that when the silver chloride content of the host grain is high, the formation of the guest grain is completed within 30 seconds, and the guest grain is slightly deformed due to recrystallization, and the chloride steel content is high. decreases (EM-10
) It was observed that guest crystals were less likely to form.

Example 6 Next, silver chloride content! A method for preparing an emulsion E of dodecahedral grains having an equivalent sphere diameter of 1 μm and having a ratio of 1 ILss to the total surface area of the (100) plane using Omolti will be described.

Emulsion E Emulsion A was desalted and washed with water three times, and inert gelatin, phenol, and water were added to redisperse the emulsion to give a silver genide concentration of 0. in7mO1/Kp Gelatin concentration 7/, riy/
TCrVc was adjusted.

This emulsion was weighed /j01 and sodium chloride O0,2fm
Add ol, inert gelatin and water, add 4f
It was dissolved at a concentration of 3%, pH 3, 1,000 kg. After that, silver nitrate 0.7 was added while maintaining the temperature at 7j'C.
100d of aqueous solution containing m01 and 0.36m of potassium bromide
olj6 and 100 d of an aqueous solution containing 11 μmol of sodium chloride O were simultaneously added to a well-stirred tank at a uniform rate over 50 minutes, washed with desalinated water, and then redispersed by adding inert gelatin, phenol, and water. Silver oxide concentration 0, 1, 7 mol/ICP,
The grains of this emulsion were tetradecahedral grains with a silver chloride content of 1% (Fig. 3(a)). Weigh, add water and convert to Hiro OCC under tooc conditions: 0.17 m o 1/potassium bromide
After adding an aqueous solution of A and an aqueous solution (corresponding to 10 moles of silver content in the host crystal), a methanol solution of PMT was added after 1 minute and 30 seconds and 3 minutes, respectively.
was added to suppress halogen conversion and recrystallization. From electron micrographs, it was observed that silver bromide guest grains were selectively bonded to the corners and edges of the dodecahedral grains containing (111) planes. (Figure 3(b) and (
C)) Example 7 Next, a method for preparing host emulsions F and G, each having a silver chloride content of tA0 mol and a cube with an equivalent sphere diameter of μm and an octahedron with some remaining (100) faces, will be described.

Host emulsion F 3 inert gelatin aqueous solution? 0m sodium chloride 0
．． ．． After adding 027 mo1 and adjusting to f) Hj, silver nitrate/mo1 was added while maintaining the preparation temperature of 700 CK.
l / ft solution 00 tl and potassium bromide O 6 hirof
mol and a solution ♂00d containing 0.373 mol of sodium chloride were simultaneously added to a well-stirred tank with SO at a constant rate over a period of minutes, and after washing with demineralized water, inert gelatin/phenol and water were added and redispersed. silver halide concentration 0.67 mol/KP, gelatin concentration 7/,
p/KpVc was adjusted. Weigh this emulsion at /20F, add 0.027 moL of sodium chloride, inert gelatin and water, and adjust the gelatin concentration to 3 T, pH 3, & room
It was dissolved so that Then, while maintaining the temperature at 7!0C, add an aqueous solution g containing 0.72 mol of silver nitrate.

Od and potassium bromide 0. Hirojmol and sodium chloride 0. an aqueous solution room containing jlAmoI, 700
For 10 minutes in a tank with good rotation,
After simultaneous addition at a constant rate and washing with demineralized water, inert gelatin, phenol and water were added and redispersed to obtain a silver halide concentration of 0.67 mol/KP, gelatin concentration of 7/, and a silver halide concentration of 0.67 mol/KP.
KPVc was adjusted.

The emulsion grains were cubic silver chlorobromide grains with a silver chloride content of lA0 mol. (Figure ≠ (a)) Host emulsion G 3% aqueous solution of inert gelatin ♂00d with 0 sodium chloride
．． After adding 027mo 1 and adjusting the pH to 3,
While maintaining the preparation temperature at 700C, prepare a solution 10 containing 100 d of silver nitrate/mol/i solution, 0°4 CJ'mol J5 of potassium bromide, and 0.37 J'mol of sodium chloride.
0d and KjO were simultaneously added to a well-stirred tank at a constant rate over a period of minutes, and after washing with demineralized water, inert gelatin/phenol and water were added and redispersed to give a silver halide concentration of 0.67 mol/KP and a gelatin concentration. 7/、ri9/K
Adjusted to t. This emulsion Na/2011 was weighed, and 2 mol of sodium chloride O,j, inert gelatin and water were added and dissolved to give a gelatin concentration of 3%, pH 3, A, and ♂00d. Then, while maintaining the temperature at 7j'C, an aqueous solution ♂00d containing 0.72m01 of silver nitrate and 00d of potassium bromide were added.
．． 4tjmol and an aqueous solution ♂θOd containing 0.73m01 of sodium chloride were simultaneously added at a constant speed over a period of minutes in a tank KjO that was well stirred at 700 rpm, and after washing with demineralized water, inert gelatin, phenol, and water were added. Addition and redispersion to obtain a silver halide concentration of 0.67 mo1/
・T・Gelatin concentration 7/, Tata/KPK adjusted.

This emulsion grain has a silver chloride content of 4L0 molt (100)
It is an octahedral particle with some remaining faces.

(Figure ψ (C)) Weigh each of emulsions F and G by 2≠7, add water and
Occ was added and Naα was added to adjust to pα/, λ6.

Potassium bromide 0, / 7 m o 1 / n
After 30 seconds for emulsion F (Fig.
1)l), and after 30 seconds for emulsion GVc (Figure μ(d)
)), 1 minute and 30 seconds later (Figure ≠ (e) ) KPMT o
'.

0! Add rmM methanol solution 4LoCC and
suppressed gene conversion and recrystallization.

For emulsion FK, which is a cubic grain emulsion, guest crystals were bonded to the corner and edge portions of the host crystal.

For emulsion GK, which is an octahedral grain emulsion with slightly (zoo) faces, it can be seen that guest crystals are joined to the edge portions near the corners in the form of protrusions.

Example g Emulsion AK Dye A/mM methanol solution 31 AOwl and 310 g were added at 5o0c and 5 minutes later potassium bromide 0. The solution was added instantaneously (about 2 seconds) at mol/41 ml, and after 7 minutes, it was washed with demineralized water and redispersed. E respectively
Let M-//, EM-/, 2.

Although EM-// had exactly the same amount of dye added as EM-2, it was observed from electron micrographs that the same effect could be obtained even if the dye was added before halogen conversion. Further, it was observed from electron micrographs that the size of the guest crystals in EM-/2 was smaller than that in EM-//.

In the example rooc, potassium bromide was added to emulsion AK at 0. I
IAmol/11 aqueous solution jd and silver nitrate O0r≠m o
l/I, aqueous solution jtl were simultaneously added at a constant rate over a period of 1 minute, and at the same time as the addition was completed, 31AOxl of dye A/mM methanol solution was added. After 7 minutes, the temperature was lowered, and the mixture was washed with demineralized water at 3!0C and re-washed. Dispersed.

This is designated as EM-/3.

As with EM-1, it is clear from electron micrographs that guest crystals are joined to the corners of the cube in the form of protrusions in EM/j.

Example 10 Dye A/mM in total amount of host emulsion A! jo 4LOxl
The mixture was added in an OC state, and the temperature was lowered 1 minute later, followed by washing with desalted water and redispersing at 3!0C to adjust the silver halide concentration and gelatin concentration to EM-/.

This will be used as an emulsion color for comparison. Further, for comparison, 1 mmol of dyes A0, 4L, and 2J'mole per 7 moI of emulsion grains were added to EM-/ to give EM/10 colors of purple. The amount of dye A added per emulsion A purple color A and EM/decachromatic purple amateur silver halide/m01 is equal to that of EM-2. Emulsion A Violet Dye A, respectively.

EM-/Purple Amateur and EM-,2 of the present invention were coated onto cellulose triacetate film at a silver content of 317 m'' and a gelatin content of 7,797 m''.

These samples were exposed to a tungsten lamp (color temperature 215'j
μK) at Fuji Photo Film Blue Cut Filter 5
Exposure was carried out using a wedge for 7710 seconds using Cj2. This exposed sample was processed using the following development recipe MAA-/
Development was carried out at 20' CIC for 3 minutes.

Sensitivity is Kabu+)+0. It is expressed as a relative value of the reciprocal of the exposure amount that gives the density of /.

MAA=/N'-methyl-p-aminophenol sulfate λ,5yL-alcorbic acid ioynabox
311! potassium bromide
add ip water
Total amount/i Table 1 The results in Table 1 also show that by bonding guest grains with a higher silver bromide content than the host grains to the host silver chlorobromide grains, the sensitivity is dramatically higher than that of the host silver chlorobromide grains. It is clear that there will be an increase. A comparison emulsion in which the surface is coated with silver bromide-rich silver halide EM/10-color purple amateur cannot achieve such an increase in sensitivity at all. Note that zero sensitivity compared to EM/10-color purple amateur is due to internal latency. This means that no surface sensitivity is observed.

Example ii EM-6 and EM-A were applied to a cellulose triacetate film in the same manner as in Example 10, and exposed and developed.
-2, EM-t, and EM-A, the molar ratio of the amount of silver in the guest crystals and the remaining host crystals was calculated from the area ratio of the two peaks in the X-ray diffraction profile, and was 0.32.0. °g3, /, ≠≠.

Table 2 As can be seen from the results, as the molar ratio of silver to the remaining host crystal of the generated guest crystal approaches 7, the sensitivity decreases.

Example 12 Emulsion A Host emulsion B, C1D under the same preparation conditions as purple dye A
Emulsions containing dyes added thereto and corresponding bonded grains EM-g, EM-ta, and EM-10 were coated in the same manner as in Example 10, and exposed and developed. Table 3 shows the sensitivity ratio of the bonded emulsion to each host emulsion.

Example/μ Host emulsion A was cooled, washed with demineralized water and redispersed to obtain thiosulfate per mol of silver.
・' ” '-' mo 1'kfa addition, j O'C
Dye AO per emulsion/mol after chemical ripening for i hours.

≠, 2 jmmol was added. This is used as emulsion A ten sulfur sensitized purple amateur for comparison.

In addition, sodium thiosulfate/X10-7 mo 1 per silver amount/mo 1 was added to the EM-2 of the present invention.
Chemically aged c/hr. For these chemical sensitizations using sodium thiosulfate, each of the above conditions gave the highest sensitivity of the emulsion. EM-2+sulfur sensitization.

Coating, exposure and development were carried out in the same manner as in Example IQ.

The results are shown in Table μ, including the case of Emulsion A Purple Amateur.

Table μ shows that even when chemical sensitization is applied, the bonded particles can achieve higher sensitivity than the host particles.

[Brief explanation of drawings]

Figure /, Figure 3, and Figure μ are electron micrographs of silver halide crystals. In Figure 1 / and Figure ≠, the magnification is 10, ooo times, and in Figure 3, the magnification is S, ooo times. . Figure 2 shows the X-ray diffraction of a silver halide emulsion, and the horizontal axis is
It represents the diffraction angle (2θ) of line diffraction and the silver bromide content in silver halide calculated from the diffraction angle, and the vertical axis represents the diffraction intensity. Patent applicant: Fuji Photo Film Co., Ltd. 1, Indication of the case: Showa to 2013, Japanese Patent Application No. 1144077, 21 Name of the invention: Silver halide photographic emulsion 3, Contact information for the person making the correction: 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106 No. 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description will be amended as follows. l) On the 2nd page/line, amend "is for." to "for the purpose of." e) Insert the entire ``method for manufacturing'' after ``particles'' on page j/line r. 3) Correct “Society” in the first line of page ♂ to “Society”. t) Correct “tutu” in line 7 of page 2 to “sotu”. In the 1st page/≠ line [at the same time or at the same time, change j to "at the same time or at the same time". 6) Page 11/! In the first line, ``Once the conjugated particles are generated quickly'' is corrected to ``When the conjugated particles are generated quickly.'' 7) Insert "enable" after "recrystallization" on the Oth line of the first page. r) In the first line of page 12, "attempt to" is amended to "attempt to". ri) Correct "ro morchi" on the first line of the first page to "7! morchi". IO) Delete "also" in the 3rd line of page 17. //) On page 77, line μ, "in excess of the soluble silver salt at that time" is corrected to "at that time". /λ) Delete [if it is added] on line j of page 17. /j) Correct "zomorchi" on page 77, line 6 to "73 morchi". 37th page, line.'' /j) Delete "700 revolutions" in the 1st line of page ≠O. /4) No. 0 page/! Correct “deyo” in line 1 to “yoyo”. /7) Delete "at 700 rpm" on the jth line of page ≠7. /? ) No. ! Insert r(NaBOz)J after "Nabox" on page O/line 7.

Claims (1)

[Claims] Silver chloride and/or face-centered cubic silver halide mixed crystal host emulsion grains containing silver chloride as a solid solution include face-centered cubic silver halide crystals with a higher silver bromide content than the average of all silver halide grains. 1. A silver halide photographic emulsion comprising grains having protrusions joined to corner portions and/or edge portions of a host crystal, and a substance having adsorption properties to silver halide.